Trace metal speciation and bioavailability in urban soils

Urban soils often contain concentrations of trace metals that exceed regulatory levels. However, the threat posed by trace metals to human health and the environment is thought to be dependent on their speciation in the soil solution rather than the total concentration. Three inactive railway yards in Montréal, Québec, were sampled to investigate the speciation and bioavailability of Cd, Cu, Ni, Pb and Zn. Soil solutions were obtained by centrifuging saturated soil pastes. In the soil solutions, up to 59% of the dissolved Cd was in its free ionic form. For Cu, Pb and Zn, organic complexes were the predominant species. Over 40% of Ni was present as inorganic complexes if the solution pH exceeded 8.1. Multiple regression analyses showed that pH and total metals in soil were significantly correlated with the activities of free metal ions, except for Cd(2+), which only had a weak correlation with soil pH. Free, dissolved and total soil metals were tested for their ability to predict metal uptake by plants in the field. However, none of these metal pools were satisfactory predictors. The results indicated that in these urban soils, trace metals were mainly in stable forms and bioavailability was extremely low.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

城市河流与湖库中痕量有机污染物的研究

通过采用ＧＤＸ－５０２富集,ＧＣ－ＭＳ分析,对城市河流、湖库中的痕量有机污染物进行分析,共检出５８种有机污染物,其中含有多种美国ＥＰＡ公布的重点污染物,从而为痕量有机污染物的研究建立了灵敏度高,分辨率好的测试方法。     

土壤铜形态和生物有效性对施用生物质炭的响应

采用改进的Tessier方法对土壤Cu形态进行分级,研究了添加生物质炭对土壤重金属Cu形态、生物有效性和小麦生长及生理指标的影响。结果表明,石灰性土壤中Cu主要以碳酸盐结合态、氧化态和残渣态形式存在,三者占土壤Cu的90%以上。添加生物质炭后,土壤中的碳酸盐结合态铜、氧化态铜含量有所减少,但不显著;有机物结合态铜含量增加了131.25%,达到极显著水平,其中主要增加了紧有机结合态。添加生物质炭在培养一定时间后（30 d后）土壤有效态铜含量降低,120天时最大降低幅度达50.66%,添加生物质炭提高了冬小麦的根系重、茎秆干重、籽粒干重和灌浆期旗叶叶绿素含量,降低了根系、茎秆和籽粒的含铜量以及超氧化物歧化酶（SOD）活性,并随着生物质炭施用量的增加有显著性差异。综合看来,生物质炭对土壤铜污染具有钝化作用。     

Runoff rates,chemical speciation and bioavailability of copper released from naturally patinated copper

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.     

Influence of particle characteristics and organic matter content on the bioavailability and bioaccumulation of pyrene by clams

Hydrophobic chemicals are known to associate with sediment particles including those from both suspended particulate matter and bottom deposits. The complex and variable composition of natural particles makes it very difficult therefore, to predict the bioavailability of sediment-bound contaminants. To overcome these problems we have previously devised a test system using artificial particles, with or without humic acids, for use as an experimental model of natural sediments. In the present work we have applied this experimental technique to investigate the bioavailability and bioaccumulation of pyrene by the freshwater fingernail clam Sphaerium corneum. The uptake and accumulation of pyrene in clams exposed to the chemical in the presence of a sample of natural sediment was also investigated. According to the results obtained, particle surface properties and organic matter content are the key factors for assessing the bioavailability and bioaccumulation of pyrene by clams.     

Impact of dissolved organic matter on bioavailability of chlorotoluron to wheat

Chlorotoluron (Chl) is a phenylurea herbicide and is widely used for controlling weeds. While it has brought great benefits to crop production, it has also resulted in contamination to ecosystem. In this study, we investigated accumulation of chlorotoluron (Chl) and biological responses of wheat plants as affected by dissolved organic matter (DOM). Wheat seedlings grown under 10 mg kg⁻¹ Chl for 4 d showed a low level of chlorophyll accumulation and damage to plasma membrane. The growth was inhibited by exposure of chlorotoluron. Treatment with 50 mg DOC kg⁻¹ DOM derived either from sludge (DOM-SL) or straw (DOM-ST) attenuated the chlorotoluron toxicity to plants. Both DOMs decreased activities of catalase, peroxidase and superoxide dismutase in Chl-treated seedlings. However, an increased glutathione S-transferases activity was observed under the same condition. Wheat plants treated with Chl in the presence of DOM accumulated less Chl than those treated with Chl alone. Moreover, in the presence of DOM, bioconcentration factor (BCF) decreased whereas translocation factors increased. Analyses with FT-IR spectra confirmed the regulatory role of DOMs in reducing Chl accumulation in wheat.     

臭氧氧化对二级出水有机物(EfOM)特性机制的影响

开展了臭氧氧化对二级出水有机物(effluent organic matter,EfOM)的去除效能研究,并进一步采用超滤分离、三维荧光光谱等方法,系统研究了不同臭氧投加量下,EfOM的分子量分布、亲疏水特性以及荧光特性的变化规律。结果表明,臭氧化去除EfOM的效果有限,但能够有效分解二级出水中具有强烈紫外吸收的有机物。此外,臭氧能优先氧化分解二级出水中大分子有机物,有效提高二级出水的可生化性。臭氧氧化过程中,分子质量(molecular weight,MW)>100 kDa的有机物组分被完全氧化分解,10 kDa< MW< 100 kDa和1 kDa< MW< 10 kD的有机物组分含量总体呈下降趋势,而MW<1 kDa的有机物组分随臭氧投加时间的延长含量不断上升。臭氧化后,EfOM中疏水组分减少,亲水组分升高;酸性组分减少。随着臭氧投量的增加,蛋白质与腐殖酸类物质的荧光吸收强度迅速下降。     

Volatile organic compounds in urban rivers and their estuaries in Osaka, Japan

The levels and distribution of 55 volatile organic compounds (VOCs) were determined by purge and trap GC-MS on water samples from 30 sites within the urban rivers and estuaries of Osaka, a populated industrialized city of Japan. Forty of 55 target VOCs listed in the US EPA Method 524.2 were detected. Dichloromethane (DCM) was found at higher levels at all of the sampling sites. The distribution of dominant VOCs followed four different patterns. First, the most common VOCs (DCM, toluene, trichloroethene and tetrachloroethene) showed concentration maxima in the river segments, and the sites of maximum concentration fluctuated due to irregular large spills and/or loadings. Second, one VOC (cis-1,2-dichloroethene) was evenly distributed in particular rivers due to fixed loadings. Both of these patterns were found in the upper and middle reaches. Third, some of VOCs (1,2,3-trichloropropane and benzene) were specific to a single industrial site and truceable to those sources. Finally, some VOCs showed no concentration maxima along the rivers and entered from multiple sources (chloroform and bromodichloromethane). Diurnal variations of VOCs at the border of the city area, receiving domestic and industrial discharges, provided information to interpret their observed downstream distribution and possible sources.     

Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.     

Fluorescence-based evidence for adsorptive binding of pyrene to effluent dissolved organic matter

Using fluorescence intensity measurements, pyrene interactions with different types of effluent dissolved organic matter (EDOM) originated from treated municipal wastewater are examined. Multiple observations show that fluorescence intensity of pyrene–EDOM solutions is non-linearly related to pyrene concentration, with distinct concave-up dependence. Testing the effect of pyrene concentration on fluorescence intensity of pyrene–EDOM solutions provides a tool to examine whether binding of an organic compound to EDOM follows linear or non-linear isotherm. Possible coupling between static and dynamic quenching effects was addressed while analyzing fluorescence data. Limited number of EDOM binding sites results in a non-linear binding isotherm such that the concept of pyrene “partitioning” between aqueous phase and “bulky” EDOM organic phase is hardly relevant. Maximal EDOM capacity for pyrene binding is estimated approximately as 0.1% w w⁻¹. Examination of the differences between the total fluorescence intensity of pyrene–EDOM solution and the fluorescence intensities of separated constituents (pyrene and EDOM) was used to illustrate the accumulation of pyrene–EDOM complexes and saturation of some EDOM binding sites. Strong interactions between pyrene and EDOM binding sites may result in pyrene distribution coefficients differing at least by a factor 3.5–7 at varying pyrene concentrations.     

矿化垃圾反应床处理垃圾渗滤液出水中的水溶性有机物

以矿化垃圾反应床处理垃圾渗滤液出水(以下简称尾水)为研究对象,采用国际上最常用的树脂联用法,对其进行梯度分离表征.研究结果表明,憎水性腐殖质对尾水COD和溶解性有机碳(DOC)的贡献分别为42.55%和45.12%,准亲水性物质对尾水中COD和DOC的贡献分别为34.89%和37.14%,憎水性腐殖质和准亲水性物质是尾水中水溶性有机物(DOM)的重要组成部分.近紫外区域吸光度分析发现,尾水中含有大量带共轭双键或苯环的有机物质,这些物质从尾水中去除后,尾水在近紫外区域的吸光度明显下降.分子量分布显示.尾水中DOM的分子量主要集中在2 000 u以下.元素分析和红外光谱结果显示,胡敏酸(HA)和富里酸(FA)带有苯环结构,存在醇羟基或酚羟基及羧酸官能团;准亲水性物质含有较多的羧酸官能团,另外存在一定置的羟基官能团,同时还可能含有三键和双键的结构.     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Influence of bacteria on Pb and Zn speciation, mobility and bioavailability in soil: A laboratory study

A soil column experiment was carried out to investigate the effects of inoculation of bacteria on metal bioavailability, mobility and potential leachability through single chemical extraction, consequential extraction and in situ soil solution extraction technologies. Results showed that bacteria inoculated, including Azotobacter chroococcum, Bacillus megaterium and Bacillus mucilaginosus, may pose both positive and negative impacts on bioavailability and mobility of heavy metals in soil, depending on the chemical nature of the metals. The activities of bacteria led to an increase of water dissolved organic carbon (DOC) concentration and a decrease of pH value, which enhanced metal mobility and bioavailability (e.g. an increase of water-soluble and HOAc-soluble Zn). On the other hand, bacteria could immobilize metals (e.g. a great reduction of water-soluble Pb) due to the adsorption by bacterial cell walls and possible sedimentation reactions with phosphate or other anions produced through bacterial metabolism.     

Spatial variation of organochlorine pesticides and dissolved organic matter in urban closed lakes

Abstract

Closed lakes located in urban parks act as sinks of organochlorine pesticides (OCPs), which have been used, for decades, as insecticides, herbicides and fungicides. The closed lakes from Bucharest, Romania, are periodically managed to prevent eutrophication and accumulation of pollutants. However, it is not known if these practices reduce or enhance the legacy pollution with OCPs. The aim of this study was to explore the spatial variation of OCPs in closed lakes. The total concentration of OCPs in water and sediments ranged between 0.0176 and 37.1?µg/L, and between 122 to 1,890?ng/g, respectively. The concentrations of OCPs were compared with the consensus-based sediment quality guidelines (SQGs) in order to evaluate the ecological risks of sediments. The highest potential adverse effects were associated with γ-HCH exposure. Periodical draining and dredging of lakes lead to the resuspension of contaminants, increasing pesticide bioavailability and accumulation in sediments. In addition, we observed that fluorescent dissolved organic matter (DOM) might influence the OCPs cycle. The quantity and character of fluorescent DOM can provide further insight into OCPs degradation. Also, this study may help urban planners to determine the state of urban waters and to find the best solution for water management.     

Potential of ultrafiltration for organic matter removal in the polymer industry effluent based on particle size distribution analysis

The purpose of the study was the experimental evaluation of ultrafiltration as a potential innovative technology for the removal of organic matter of around 15,000 mg chemical oxygen demand (COD) per liter in the polymer industry wastewater. Particle size distribution (PSD) analysis served as the major experimental instrument along with conventional chemical settling. Biodegradation characteristics of the remaining COD after ultrafiltration were determined by model interpretation of the corresponding oxygen uptake rate (OUR) profile. The study first involved a detailed characterization of the polymer wastewater including PSD analysis of the COD content. Chemical treatability was investigated using lime alone and with ferric chloride as coagulants followed with a PSD assessment of the chemically settled effluent. Modeling of the OUR profile generated by the ultrafiltration effluent defined related biodegradation kinetics and provided information on the overall COD removal potential. PSD analysis indicated that more than 70 % of the total COD accumulated in the 220- to 450-nm size range. It indicated that ultrafiltration was potentially capable of removing more than 90 % of the COD with an effluent lower than 1,500 mg COD/L. Chemical settling with 750 mg/L of FeCl₃ dosing at a pH of 7.0 provided a similar performance. The ultrafiltration effluent included mainly hydrolysable COD and proved to be biodegradable, with the process kinetics compatible with domestic sewage. PSD evaluation proved to be a valuable scientific instrument for underlining the merit of ultrafiltration as the appropriate innovative technology for polymer wastewater, removing the major portion of the COD in a way that is suitable for recovery and reuse and producing a totally biodegradable effluent.     

人工纳米颗粒输入对稻田土壤Cd形态转化及生物有效性的影响

进入农田土壤的人工纳米颗粒对土壤中重金属迁移转化及毒性的影响仍不明确。通过模拟稻田淹水-落干过程,研究了二氧化钛（TiO2-NPs）、氧化锌（ZnO-NPs）和多壁碳纳米管（MWCNTs）3种典型人工纳米颗粒对水稻土中重金属Cd赋存形态及生物有效性的影响。结果表明,3种纳米颗粒的添加均引起了土壤pH的增加;TiO2-NPs和ZnO-NPs添加能够显著降低土壤中酸可提取态Cd含量;ZnO-NPs的添加对土壤中铁锰氧化物结合态和有机结合态Cd的含量也有明显降低,但不同浓度处理间Cd含量并无显著差异;MWCNTs对土壤Cd形态转化无显著影响。与对照处理相比,添加TiO2-NPs的处理土壤中,CaCl2和DTPA提取态Cd含量分别降低了13.9%~17.5%和5.4%~8.9%,降幅均与TiO2-NPs添加浓度成正比。添加ZnO-NPs的土壤中,DTPA提取态Cd的含量降幅在8.4%~18.7%之间,降低幅度与ZnO-NPs添加浓度成反比。     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.